Colored speckles for use in granular detergents

ABSTRACT

This invention relates to non-bleeding, non-staining colored speckles for use in granular or powdered detergents such as laundry detergents and automatic dishwashing detergents. The colored speckles are comprised of a salt or salt-containing carrier and a coloring agent and are characterized as being substantially uniformly colored throughout the cross-sectional volume of the speckle.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/349,393, entitled “Colored Speckles Having Delayed ReleaseProperties” which was filed on May 28, 2010.

FIELD OF THE INVENTION

This invention relates to non-bleeding, non-staining colored specklesfor use in granular or powdered detergents such as laundry detergentsand automatic dishwashing detergents. The colored speckles are comprisedof a salt or salt-containing carrier and a coloring agent and arecharacterized as being substantially uniformly colored throughout thecross-sectional volume of the speckle.

BACKGROUND OF THE INVENTION

Recently there has been an increasing trend towards the incorporation ofcolored speckles into particulate detergent compositions and otherconsumer products. Dyes and pigments have been widely used to producecolored speckles that serve aesthetic purposes only. Novel effects suchas release of color into the wash water and hueing of fabrics, however,tend to require higher colorant loadings. There is, particularly atthese higher colorant loadings, a fabric staining risk associated withdye and pigment use. Thus, the need exists for colored speckles for usein detergent compositions and other consumer products that can serveboth an aesthetic purpose and also provide the novel effects of releaseof color and hueing of fabrics without staining the substrates that comeinto contact with the colored speckles.

Additionally, the inclusion of colored speckles in granulated laundrydetergents presents the problem of bleeding or transferring onto thepowdered detergent surrounding the speckle. This results in the basepowder becoming colored, which is a highly undesirable effect. Thus, theneed exists for colored speckles for use in detergent compositions whichdo not bleed or transfer to the surrounding base powder.

The problems associated with previous attempts by others to includecolored speckles in detergents include (a) fabric staining from thecolorant used in the speckles and (b) bleeding and transferring of thecolorant to the surrounding detergent powder. Thus, there exists acontinual need for colored speckles that provide aesthetic appeal todetergent compositions, visible coloration to wash water, and hueingeffects to whiten fabrics without bleeding onto the surroundingdetergent granules and without staining the fabrics. The presentdisclosure addresses and overcomes these problems.

The colored speckles of the present disclosure are ideally suited forproviding color to various compositions including, but not limited togranular detergent compositions (such as laundry detergentcompositions). The colored speckles may provide non-staining,aesthetically-pleasing features to textile substrates treated therewith.They also resist bleeding or transferring to the surrounding detergentcomposition. Furthermore, the colored speckles of the present disclosureprovide release of color, or other actives, from the salt orsalt-containing carrier and provide desirable color to the wash water.For these reasons, and others that will be described herein, the presentcolored speckles represent a useful advance over the prior art.

BRIEF SUMMARY OF THE INVENTION

Provided herein is a colored speckle comprising: a) a majority by weightof at least one salt or salt-containing carrier material; and b) atleast one coloring agent; wherein the at least one carrier material andthe at least one coloring agent form a carrier-coloring agent composite,and wherein the carrier-coloring agent composite comprises across-sectional volume that is substantially uniformly colored by the atleast one coloring agent.

Yet another alternative includes a colored speckle comprising: a) amajority by weight of at least one sodium carbonate-containing carriermaterial; and b) at least one polymeric coloring agent; wherein the atleast one sodium carbonate-containing carrier material and the at leastone polymeric coloring agent form a carrier-coloring agent composite,and wherein the carrier-coloring agent composite comprises across-sectional volume that is substantially uniformly colored by the atleast one polymeric coloring agent.

Further provided herein is a colored speckle comprising: a) a majorityby weight of compacted soda ash carrier material; and b) at least onecoloring agent; wherein the at least one compacted soda ash carriermaterial and the at least one coloring agent form a carrier-coloringagent composite, and wherein the carrier-coloring agent compositecomprises a cross-sectional volume that is substantially uniformlycolored by the at least one coloring agent.

DETAILED DESCRIPTION OF THE INVENTION

All U.S. and foreign patents and patent applications disclosed in thisspecification are hereby incorporated by reference in their entirety.

The present disclosure relates to non-bleeding and non-staining coloredspeckles for use in granular detergent compositions. The speckles arefurther characterized in that they exhibit color on the outer surface ofthe speckle, as well as throughout the cross-section of the speckle. Ingeneral, this means that if one were to cut the colored speckle in halfand examine a cross-section of the speckle, the color would appear to besubstantially, uniformly distributed throughout that cross-section.Thus, the colored speckles may be described herein as beingsubstantially, uniformly colored throughout the body of the speckle. Thecolored speckle may also be described herein as being substantially,uniformly colored throughout the cross-sectional volume of the speckle.The colored speckles of the present invention may also find applicationsin other consumer products outside powdered or granular detergentcompositions.

The colored speckles are comprised of salt or salt-containing granulesand a coloring agent. The salt or salt-containing granules act as acarrier for the coloring agent. Herein, the present disclosure describesa colored speckle and a method for making the colored speckle whichprovides release of the coloring agent in wash water while reducing, oreven eliminating, color migration or bleed on powdered detergent.

The term “non-staining” as used herein, generally refers to a coloringagent, or a composition that contains such a coloring agent, that may bewashed or removed from substrate surfaces (e.g. skin, fabric, wood,concrete) with relatively little effort and without staining thesubstrate to an appreciable extent.

The term “non-bleeding,” as used herein, generally refers to a coloringagent-containing composition that does not substantially color thematerial surrounding the composition under conditions wherein thematerial is not intended to be colored. For example, the coloredspeckles of the present invention will generally be considered to be“non-bleeding” if the colored speckles fail to substantially color thesurrounding powdered detergent in its unused state (i.e. while itremains in the package).

The term “water-insoluble” or “minimally water soluble,” as used herein,generally refers to a material whose solubility in water at 20° C. and 1atmosphere of pressure is less than 3 grams/100 ml of water.

The term “water-soluble,” as used herein, generally refers to a materialwhose solubility in water at 20° C. and 1 atmosphere of pressure isgreater than 3 grams/100 ml of water.

The term “salt” as used herein, generally refers to ionic compoundscomprised of both cations (positively charged ions) and anions(negatively charged ions) so that the product is electrically neutral(without a net charge). These component ions may be inorganic or organicions, monatomic or polyatomic, monovalent or multivalent.

The term “salt containing” as used herein, generally refers to aphysical blend or mixture of a salt and some other component/components(organic or inorganic) that is either in the powdered form (may bereferred to herein as the carrier material) or in a granulated form (maybe referred to herein as granules or carrier granules). These “other”components may be salts (water-soluble salts as well as water-insolubleor minimally water-soluble salts) and other organic or inorganicmaterials (for example: minerals, chalk, mica, clays, etc).

The term “carrier-coloring agent composite” as used herein refers to amaterial or “carrier” (salt or other, single component ormulti-component, powder or granule) that has at least some part of itssurface in contact with a color or coloring agent. The color or coloringagent may be adsorbed to the surface of the carrier.

Carrier Material

The carrier material is preferably in the form of a salt orsalt-containing granule. The colored speckle may be comprised of amajority by weight of the carrier material. The material used to producethe salt or salt-containing granule may be characterized as beingcomprised of at least one water-soluble salt or a mix of at least onewater-soluble salt and at least one water-insoluble material. Thecarrier material may be characterized as being a porous material, anon-porous material, or a combination of porous and non-porousmaterials.

The salt or salt-containing carrier material may be selected from atleast one of, but is not limited to, the following materials: lithiumsalts, sodium salts (such as but not limited to sodium sulfate, sodiumbisulfate, sodium carbonate, sodium tripolyphosphate, sodiumpolyphosphate, sodium phosphates, monosodium phosphate, sodium hydrogenphosphate, sodium dihydrogen phosphate, sodium chloride, sodiumbicarbonate, sodium percarbonate, sodium nitrate, sodium nitrite, sodiumthiosulfate, sodium acetate, sodium bromide, sodium chlorate, sodiumperchlorate, sodium chromate, sodium dichromate, sodium iodide, sodiumiodate, sodium oxalate, sodium silicate, sodium sulfide, sodium sulfite,sodium bisulfite, sodium citrate, sodium malate, sodium stearate, sodiumlauryl sulfate, sodium benzoate, sodium bromate, sodium formate, sodiumpyrophosphate, sodium selenate, sodium periodate, sodium molybdate,sodium hydrates, and mixtures thereof), potassium salts (such as but notlimited to potassium sulfate, potassium chloride, potassium acetate,potassium chlorate, potassium chromate, potassium iodide, potassiumnitrate, potassium nitrite, potassium thiosulfate, potassium selenate,potassium formate, potassium bromide, potassium carbonate, potassiumbicarbonate, potassium persulfate, potassium phosphate, potassiumpermanganate, potassium iodate, potassium fluoride, potassium bisulfate,potassium thiocyanate, potassium dihydrogen phosphate, potassiumdichromate, potassium cyanide, potassium bromate, potassium benzoate,potassium arsenate, potassium azide, potassium oxalate, potassiumsilicate, potassium sulfite, potassium citrate, potassium hydrates, andmixtures thereof), rubidium salts, cesium salts, francium salts,beryllium salts, magnesium salts (such as but not limited to magnesiumsulfate, magnesium chloride, magnesium acetate, magnesium chlorate,magnesium chloride, magnesium chromate, magnesium iodide, magnesiumnitrate, magnesium thiosulfate, magnesium selenate, magnesiumperchlorate, magnesium formate, magnesium bromide, magnesium sulfite,magnesium citrate, magnesium fluorosilicate, magnesium hydrates, andmixtures thereof), calcium salts (such as but not limited to calciumchloride, calcium acetate, calcium chlorate, calcium chromate, calciumiodide, calcium nitrate, calcium formate, calcium bromide, calciumbicarbonate, calcium permanganate, calcium bromate, calcium perchlorate,calcium hydrates, and mixtures thereof), strontium salts, barium salts,radium salts, scandium salts, titanium salts, zirconium salts, hafniumsalts, vanadium salts, chromium salts, molybdenum salts, tungsten salts,manganese salts, iron salts (II & III), ruthenium salts, cobalt salts,iridium salts, nickel salts, palladium salts, platinum salts, copper (I& II) salts, silver salts, gold salts, zinc salts, cadmium salts, boronsalts, aluminum salts, thallium salts, antimony salts, bismuth salts,ammonium salts, quaternary ammonium salts, pyridinium salts, nitratesalts (such as but not limited to sodium nitrate, ammonium nitrate,magnesium nitrate, aluminum nitrate, barium nitrate, cadmium nitrate,calcium nitrate, chromium nitrate, cobalt nitrate, cupric nitrate, ironnitrate, lead nitrate, potassium nitrate, nickel nitrate, silvernitrate, strontium nitrate, zinc nitrate, nitrate hydrates, and mixturesthereof), nitrite salts, chloride salts (such as but not limited tosodium chloride, ammonium chloride, magnesium chloride, aluminumchloride, antimony chloride, barium chloride, cadmium chloride, calciumchloride, chromium chloride, cobalt chloride, cupric chloride, ferricchloride, ferrous chloride, mercury chloride, nickel chloride, potassiumchloride, strontium chloride, zinc chloride, chloride hydrates, andmixtures thereof), chlorate salts (such as but not limited to sodiumchlorate, ammonium chlorate, magnesium chlorate, aluminum chlorate,barium chlorate, cadmium chlorate, calcium chlorate, cobalt chlorate,cupric chlorate, lead chlorate, potassium chlorate, silver chlorate,strontium chlorate, zinc chlorate, chlorate hydrates, and mixturesthereof), chromate salts (such as but not limited to sodium chromate,ammonium chromate, magnesium chromate, calcium chromate, copperchromate, iron chromate, potassium chromate, chromate hydrates, andmixtures thereof), cyanate salts, cyanide salts, fluoride salts, acetatesalts (such as but not limited to sodium acetate, ammonium acetate,magnesium acetate, aluminum acetate, barium acetate, cadmium acetate,calcium acetate, chromium acetate, cobalt acetate, cupric acetate, leadacetate, nickel acetate, potassium acetate, strontium acetate, zincacetate, acetate hydrates, and mixtures thereof), bromide salts (such asbut not limited to sodium bromide, ammonium bromide, magnesium bromide,aluminum bromide, barium bromide, cadmium bromide, calcium bromide,chromium bromide, cobalt bromide, cupric bromide, ferric bromide,ferrous bromide, lead bromide, nickel bromide, potassium bromide,strontium bromide, zinc bromide, bromide hydrates, and mixturesthereof), boride salts, iodide salts (such as but not limited to sodiumiodide, aluminum iodide, ammonium iodide, arsenic iodide, magnesiumiodide, barium iodide, cadmium iodide, calcium iodide, cobalt iodide,iron iodide, nickel iodide, potassium iodide, strontium iodide, zinciodide, iodide hydrates, and mixtures thereof), sulfate salts (such asbut not limited to magnesium sulfate, sodium sulfate, cadmium sulfate,aluminum sulfate, ammonium sulfate, chromium sulfate, cobalt sulfate,cupric sulfate, iron sulfate, nickel sulfate, potassium sulfate, zincsulfate, sulfate hydrates, and mixtures thereof), sulfite salts (such asbut not limited to ammonium sulfite, potassium sulfite, sodium sulfite,magnesium sulfite, sulfite hydrates, and mixtures thereof), sulfidesalts (such as but not limited to ammonium sulfide, potassium sulfide,sodium sulfide, sulfide hydrates, and mixtures thereof), sulfamatesalts, sulfonate salts, carbonate salts (such as but not limited tosodium carbonate, sodium percarbonate, potassium carbonate, ammoniumcarbonate, carbonate hydrates, and mixtures thereof), bicarbonate salts,ascorbate salts, phosphate salts (such as but not limited to ammoniumphosphate, potassium phosphate, sodium phosphate, sodiumtripolyphosphate, phosphate hydrates, and mixtures thereof),polyphosphate salts (such as but not limited to sodiumtripolyphosphate), citrate salts (such as but not limited to potassiumcitrate, sodium citrate, magnesium citrate, citrate hydrates, andmixtures thereof), oxides (such as metal oxides, zinc oxide, leaded zincoxide, antimony oxide, and mixtures thereof), hydroxides, cyanide salts,permanganates, adipates, benzoates, fluorides, silicates (such as butnot limited to sodium silicate, potassium silicate, barium silicates,silicate hydrates, and mixtures thereof), lactates, malates,perchlorates, persulfates, oxalates (such as but not limited to sodiumoxalate, chromium oxalate, iron oxalate, potassium oxalate, oxalatehydrates, and mixtures thereof), organic salts, alkali metalaluminosilicates, borax, clay, silica, zeolite, diatomaceous earth,mica, talc, chalk, gypsum, lithopone, titanium dioxide, barytes, silicaflatting agents, and the like, and combinations thereof.

Soda ash (e.g. sodium carbonate) may be a preferred carrier material forthe colored speckles of the present invention. In one aspect, soda ashthat has been compacted via a wet or a dry granulation process, asfurther described herein, to form compacted soda ash carrier materialmay be used as the carrier material.

Compacted soda ash carrier material may be formed by exposing the sodaash carrier material to pressure or force, which causes the soda ashmaterial to be compacted or pressed together into a larger form orshape; this larger form or shape is subsequently broken apart bymechanical agitation to form smaller pieces which are then passedthrough a sieve for particle size selection. The step of applyingpressure or force to the soda ash may be achieved by passing the sodaash carrier material between at least two cylindrical rollers in aprocess known as roller compaction. To form colored speckles comprisedof colored compacted soda ash, a coloring agent may be applied to thesoda ash carrier material prior to the compaction process. In anotheraspect, other carrier materials disclosed herein may also be formed intocompacted carrier material by these methods.

It may be preferable that the carrier material exhibits a particularrange of particle size, as determined, for example, by sievingtechniques according to ASTM D1921-06 (“Standard Test Method ForParticle Size (Sieve Analysis) of Plastic Materials”). Alternativemethods known to those skilled in the art may also be utilized fordetermining particle size. For example, other sieving techniques may beused or electronic laboratory equipment known for determining particlesize may alternatively be employed. For the carrier materials of thepresent invention, it may be preferably that the carrier materialsexhibit an average particle size of about 0.1 mm to about 2 mm, morepreferably an average particle size of about 0.3 mm to about 1.5 mm.

Coloring Agent

The coloring agent of the present invention is preferably a polymericcolorant. The term “polymeric colorant” generally refers to a coloranthaving at least one chromophore portion attached to at least oneoligomeric or polymeric chain, wherein the chain has at least threerepeating units. The oligomeric or polymeric constituent can be bound tothe chromophore via any suitable means, such as a covalent bond, anionic bond, or suitable electrostatic interaction. Generally, thepolymeric colorant may be characterized by having an absorbance in therange of between about 300 nanometers and about 900 nanometers, asmeasured by UV-vis spectroscopy.

As a function of its manufacturing process, the polymeric colorant has amolecular weight that is typically represented as a molecular weightdistribution. Accordingly, the molecular weight of the polymericcolorant is generally reported as an average molecular weight, asdetermined by its molecular weight distribution.

The chromophore group of the colorant may vary widely, and may includecompounds characterized in the art as dyestuffs or as pigments. Theactual group used will depend to a large extent upon, for instance, thedesired color and colorfastness characteristics. The chromophore groupmay be attached to at least one polyalkyleneoxy-substituent through asuitable linking moiety of nitrogen, oxygen, sulfur, etc.

Examples of chromophore groups include nitroso, nitro, azo (includingmonoazo, disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine andmetal complexes thereof), stilbene, bis-stilbene, biphenyl,oligophenethylene, fluorene, coumarin, napthalamide, diarylmethane,triarylmethane, xanthene acridine, quinoline, methine (includingpolymethine), thiazole, indamine, indophenol, azine, thiazine, oxazine,aminoketone, hydroxyketone, anthraquinone (including anthrapyrazolines,anthrone, anthrapyridone, anthrapyrimidine, flavanthrone, pyranthrone,benzanthrone, perylene, perinone, naphthalimide and other structuresformally related to anthraquinone), indigoid (including thioindigoid),phthalocyanine chromophore groups, and mixtures thereof.

Examples of suitable polymeric chains are polyalkyleneoxy chains. Theterm “polyalkyleneoxy,” as used herein, generally refers to molecularstructures containing the following repeating units: —CH₂CH₂O—,CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—,—CH₂CH(CH₂CH₃)O—CH₂CH₂CH(CH₃)O—, CH₂CH(O—)(CH₂O—), and any combinationsthereof.

Typical of such groups which may be attached to the chromophore groupare the polymeric epoxides, such as the polyalkylene oxides andcopolymers thereof. Typical polyalkylene oxides and copolymers of samewhich may be employed to provide the colorants include those made fromalkylene oxide monomers containing from two to twenty carbon atoms, ormore preferably, from two to six carbon atoms. Examples include:polyethylene oxides; polypropylene oxides; polybutylene oxides;oxetanes; tetrahydrafurans; copolymers of polyethylene oxides,polypropylene oxides and polybutylene oxides; and other copolymersincluding block copolymers, in which a majority of the polymericsubstituent is polyethylene oxide, polypropylene oxide and/orpolybutylene oxide. Further, such polyalkyleneoxy group may have anaverage molecular weight in the range of from about 132 to about 10,000,preferably from about 176 to about 5000.

It is to be understood that because the colorants may not ordinarily bechemically bound to the carrier, the precise chemical identity of theend group on the polyalkyleneoxy group may not be critical insofar asthe proper functioning of the colorant is concerned in the composition.With this consideration in mind, certain most preferred colorants willbe defined wherein certain end groups will be identified. Suchrecitation of end groups is not to be construed as limiting theinvention in its broader embodiments in any way. According to such amost preferred embodiment the colorants may be characterized as follows:R{A[(alkyleneoxy constituent)_(n)R₁]_(m)}_(x)wherein R is an organic chromophore group, A is a linking moiety in saidorganic chromophore group selected from the group consisting of N, O,SO₂ or CO₂, the alkylene moiety of the alkyleneoxy constituent containsfrom 2 to about 4 carbon atoms, n is an integer of from 2 to about 230,m is 1 when A is O, SO₂, CO₂ and 1 or 2 when A is N, x is an integer offrom 1 to 5, and the product of n times x times m (n·m·x) is from 2 toabout 230, and R₁ is a member of the group consisting of

and sulfonates and sulfates of each of the members of said group,wherein R₂ is H, an alkyl radical containing up to about 20 carbon atomsor carboxy-terminated alkyl radical containing up to about 20 carbonatoms, j and k are OH, OM or OR₃ wherein M is a cation moiety of analkali metal, an alkaline earth metal, transition metal, e.g., nickel,etc. or ammonium, and R₃ is an alkyl radical containing up to about 20carbon atoms.

The oligomeric constituent can be any suitable constituent including,but not limited to, oligomeric constituents selected from the groupconsisting of (i) oligomers comprising at least three monomers, orrepeating units, selected from the group consisting of C₂-C₂₀alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii) aromaticor aliphatic oligomeric esters conforming to structure (I)

and (iii) combinations of (i) and (ii). In structure (I), R₂ and R₃ areindependently selected from the group consisting of hydrogen and C₁-C₁₀alkyl groups, f is an integer between and including 1 and 10, and g isany positive integer or fraction between and including 1 and 20. As willbe understood by those of ordinary skill in the art, suitable values forg include both integers and fractions because the length of theoligomeric constituent on the individual polymeric colorant moleculesmay vary. Thus, the value for g represents an average length of theester chain for a given sample or collection of polymeric colorantmolecules. In certain embodiments, the polymeric colorant can compriseone or more oligomeric constituents consisting of three or more ethyleneoxide monomer groups.

Exemplary polymeric colorants include Liquitint® polymeric colorants,Cleartint® polymeric liquid concentrate colorants, Reactint® polymericcolorants, and Palmer® polymeric colorants, all of which are availablefrom Milliken Chemical, a division of Milliken & Company of Spartanburg,S.C. Liquitint® polymeric colorants are characterized in that they arewater soluble, non-staining, colorants. They are widely used in laundrydetergents, fabric softeners, and other consumer and industrial cleaningproducts. Liquitint® polymeric colorants are generally bright liquidcolorants which, depending on the specific colorant, exhibit varyingdegrees of solubility in water. These colorants may also becharacterized as being generally compatible with other chemicals presentin their end-use formulations and are typically easy to handle.Liquitint® polymeric colorants may be used to provide color in bothaqueous and solid systems. The unique polymeric nature of Liquitint®polymeric colorants provides reduced staining to skin, textiles, hardsurfaces, equipment, and the like.

Cleartint® polymeric liquid concentrate colorants are specially designedliquid colorants often used for coloring clarified polypropylenearticles. These colorants may be incorporated into polypropylene resinseasily without detrimentally affecting the clarity of the article toprovide transparent, clear and brightly colored polypropylene articles.Cleartint® liquid concentrate polymeric colorants are oligomericcoloring materials which combine the exceptional aesthetics of dyes withthe migration resistance of pigments. These colorants may be used aslight tints to mask residual haze, or they may be used for deep, richshades that are not possible with pigment colorants. Cleartint® liquidconcentrate polymeric colorants allow clarified polypropylene to rivalthe beauty of higher cost plastic materials. The technical and physicalproperty benefits of clarified polypropylene may be exploited withoutsacrificing product aesthetics.

Reactint® polymeric colorants are liquid polymeric colorants useful forcoloring polyurethane and other thermoset resins. These colorants arereactive polymeric colorants that consist of chromophores which arechemically bound to polyols. This arrangement allows the polymericcolorant to react into the polyurethane polymer matrix. Unlike pigmentpastes, which are dispersions of solid particles in a liquid carrier,Reactint® polymeric colorants are 100% homogeneous liquids that aresoluble in polyol and will not settle over time. Because of this pureliquid and easy to disperse nature, it is possible to blend Reactint®colorants in-line and on-the-fly, while producing polyurethane foams andresins.

Palmer® polymer colorants are liquid colorants specially developed foruse in washable applications, such as in markers, paints and other artproducts. They contain no heavy metals, are non-toxic, and haveexcellent non-staining properties on skin, fabric and other surfaces.Palmer® polymeric colorants have very good compatibility with aqueousink formulations and provide bright colors.

It is also contemplated to be within the scope of the present inventionthat other colorants may be utilized as the coloring agent. For example,a colorant selected from one or more of the following classes may besuitable for use as the coloring agent in the colored speckle: aciddyes, basic dyes, direct dyes, solvent dyes, vat dyes, mordant dyes,indigoid dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescentdyes; pigments, both organic and inorganic; natural colorants; and thelike.

Optional Additive—Release-Rate Modifier (Water-Soluble Salt)

A release-rate modifier such as a water-soluble salt may optionally beincluded in the colored speckle of the present invention. Awater-soluble salt (also referred to herein as the “release-ratemodifier”) is generally used to effectuate the delayed release of thecoloring agent from the carrier-coloring agent composite material.Without being bound by theory, this activity occurs through a reactionbetween the water-soluble salt (release-rate modifier) and the(water-soluble) salt present in the carrier agent material or granule toform a water-insoluble salt coating thereon. Thus, a colored specklehaving delayed color release properties is made.

There may be multiple water-soluble salts present in the carrier granulethat could react with the release-rate modifier to give the sameinsoluble precipitate (for example if aqueous magnesium sulfate isapplied to granules containing a mixture of soda ash and potassiumcarbonate; both will react with the magnesium sulfate to give the sameprecipitate of magnesium carbonate) or multiple insoluble precipitates(for example if aqueous magnesium sulfate is applied to granulescontaining a mixture of soda ash and sodium phosphate; each will reactwith the magnesium sulfate to give distinct precipitates of magnesiumcarbonate and magnesium phosphate respectively) or there may be at leastone such water-soluble carrier salt present (to react with therelease-rate modifier). Similarly, a carrier material or granule/specklemay be treated with a solution of multiple release-rate modifiers/atleast one release rate modifier.

The mechanism by which two water-soluble salts combine to form awater-insoluble precipitate (salt) is an example of adisplacement/replacement reaction. When two water-soluble salts, AB andCD, are dissolved in water, they tend to dissociate and yield a solutionof A⁺, B⁻, C⁺, and D⁻ ions (monovalent ions are used herein forexemplary purposes and should not be considered limiting). Now, byfurther chemical reaction, these ions may combine to give AD and CB.Additionally, it is possible that one of the salts (AD or CB) may beinsoluble (or minimally soluble) in water. Thus, it will precipitate outof solution.

As one non-limiting example of a displacement/replacement reaction, thecombination of sodium carbonate and magnesium sulfate (in the presenceof water) results in the formation of a white precipitate of magnesiumcarbonate (due to its minimal solubility in water at room temperature).In the same way, when an aqueous solution of magnesium sulfate is addedto soda ash granules (colored or un-colored), an insoluble/minimallysoluble precipitate of magnesium carbonate is generated which depositson/coats the surface of the soda ash granules and delays dissolution ofthe granules themselves and/or consequently delays the release ofwhatever active (such as a coloring agent) may be present on orwithin/throughout the soda ash material.

When added to an aqueous solution, these treated colored speckles (suchthat an insoluble salt coating is present on their surface) typicallydissolve or disintegrate at a slower rate than speckles that have noinsoluble salt deposited on their surface. Accordingly, the release ofcoloring agent (or other active) contained therein occurs at a slowerrate than speckles that have no insoluble salt deposited on theirsurface. The water-insoluble salt coating generally remains intact (forthe period of observation of 10 to 15 minutes) and is left behind as aby-product of the colored speckle.

The water-soluble salt to be used as a release rate modifier may be anymaterial that is capable of reacting with at least one salt in thecarrier material to form or precipitate a water-insoluble or minimallywater-soluble salt or salts. The choice of water-soluble salt to be usedas release-rate modifier may be dependent on the type of salt or saltspresent in the carrier granule used to make the colored speckles. Acarrier material or granule/speckle may be treated with a singlerelease-rate modifier or multiple release-rate modifiers (in otherwords, at least one release rate modifier).

The at least one water-soluble salt may be selected from the groupconsisting of water-soluble salts of beryllium, magnesium, calcium,strontium, barium, lead, radium, scandium, titanium, zirconium, hafnium,vanadium, chromium, molybdenum, tungsten, manganese, iron(II & III),ruthenium, cobalt, iridium, nickel, palladium, platinum, mercury, copper(I & II), silver, gold, zinc, cadmium, boron, aluminum, thallium,antimony, bismuth, pyridinium, ammonium, quaternary ammonium, nitrate,nitrite, hydroxide, oxide, oxalate, phosphate, silicate, sulfide,carbonate, chromate, chlorate, sulfate, sulfite, acetate, citrate,iodide, bromide, chloride, hydrates thereof, and mixtures thereof.

Water-soluble salts of magnesium may be selected from the groupconsisting of magnesium sulfate, magnesium chloride, magnesium acetate,magnesium chlorate, magnesium chromate, magnesium iodide, magnesiumnitrate, magnesium perchlorate, magnesium bromide, magnesium sulfite,magnesium citrate, magnesium hydrates, and mixtures thereof.

Water-soluble salts of sodium may be selected from the group consistingof sodium sulfate, sodium bisulfate, sodium carbonate, sodiumtripolyphosphate, sodium polyphosphate, sodium phosphates, monosodiumphosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate,sodium chloride, sodium bicarbonate, sodium percarbonate, sodiumnitrate, sodium nitrite, sodium acetate, sodium bromide, sodiumchlorate, sodium perchlorate, sodium chromate, sodium dichromate, sodiumiodide, sodium iodate, sodium oxalate, sodium silicate, sodium sulfide,sodium sulfite, sodium bisulfite, sodium citrate, sodium stearate,sodium benzoate, sodium bromate, sodium formate, sodium hydrates, andmixtures thereof.

Water-soluble salts of potassium may be selected from the groupconsisting of potassium sulfate, potassium chloride, potassium acetate,potassium chlorate, potassium chromate, potassium iodide, potassiumnitrate, potassium nitrite, potassium formate, potassium bromide,potassium carbonate, potassium bicarbonate, potassium persulfate,potassium phosphate, potassium iodate, potassium fluoride, potassiumbisulfate, potassium dihydrogen phosphate, potassium dichromate,potassium bromate, potassium benzoate, potassium oxalate, potassiumsilicate, potassium sulfite, potassium citrate, potassium hydrates, andmixtures thereof.

Water-soluble salts of calcium may be selected from the group consistingof calcium chloride, calcium acetate, calcium chlorate, calciumchromate, calcium iodide, calcium nitrate, calcium formate, calciumbromide, calcium bicarbonate, calcium permanganate, calcium bromate,calcium perchlorate, calcium hydrates, and mixtures thereof.

Water-soluble chloride salts may be selected from the group consistingof sodium chloride, ammonium chloride, magnesium chloride, aluminumchloride, antimony chloride, barium chloride, cadmium chloride, calciumchloride, chromium chloride, cobalt chloride, cupric chloride, ferricchloride, ferrous chloride, mercury chloride, nickel chloride, potassiumchloride, strontium chloride, zinc chloride, chloride hydrates, andmixtures thereof.

Water-soluble sulfate salts may be selected from the group consisting ofmagnesium sulfate, sodium sulfate, cadmium sulfate, aluminum sulfate,ammonium sulfate, chromium sulfate, cobalt sulfate, cupric sulfate, ironsulfate, nickel sulfate, potassium sulfate, zinc sulfate, sulfatehydrates, and mixtures thereof.

Water-soluble sulfide salts may be selected from the group consisting ofammonium sulfide, potassium sulfide, sodium sulfide, sulfide hydrates,and mixtures thereof.

Water-soluble carbonate salts may be selected from the group consistingof sodium carbonate, sodium percarbonate, potassium carbonate, ammoniumcarbonate, carbonate hydrates, and mixtures thereof.

Water-soluble phosphate salts may be selected from the group consistingof ammonium phosphate, potassium phosphate, sodium phosphate, sodiumtripolyphosphate, phosphate hydrates, and mixtures thereof.

Water-soluble silicates may be selected from the group consisting ofsodium silicate, potassium silicate, barium silicates, silicatehydrates, and mixtures thereof.

Water-soluble acetate salts may be selected from the group consisting ofsodium acetate, ammonium acetate, magnesium acetate, aluminum acetate,barium acetate, cadmium acetate, calcium acetate, chromium acetate,cobalt acetate, cupric acetate, lead acetate, nickel acetate, potassiumacetate, strontium acetate, zinc acetate, acetate hydrates, and mixturesthereof.

Water-soluble bromide salts may be selected from the group consisting ofsodium bromide, ammonium bromide, magnesium bromide, aluminum bromide,barium bromide, cadmium bromide, calcium bromide, chromium bromide,cobalt bromide, cupric bromide, ferric bromide, ferrous bromide, leadbromide, nickel bromide, potassium bromide, strontium bromide, zincbromide, bromide hydrates, and mixtures thereof.

Water-soluble chlorate salts may be selected from the group consistingof sodium chlorate, ammonium chlorate, magnesium chlorate, aluminumchlorate, barium chlorate, cadmium chlorate, calcium chlorate, cobaltchlorate, cupric chlorate, lead chlorate, potassium chlorate, silverchlorate, strontium chlorate, zinc chlorate, chlorate hydrates, andmixtures thereof.

Water-soluble chromate salts may be selected from the group consistingof sodium chromate, ammonium chromate, magnesium chromate, calciumchromate, copper chromate, iron chromate, potassium chromate, chromatehydrates, and mixtures thereof.

Water-soluble iodide salts may be selected from the group consisting ofsodium iodide, aluminum iodide, ammonium iodide, arsenic iodide,magnesium iodide, barium iodide, cadmium iodide, calcium iodide, cobaltiodide, iron iodide, nickel iodide, potassium iodide, strontium iodide,zinc iodide, iodide hydrates, and mixtures thereof.

Water-soluble nitrate salts may be selected from the group consisting ofsodium nitrate, ammonium nitrate, magnesium nitrate, aluminum nitrate,barium nitrate, cadmium nitrate, calcium nitrate, chromium nitrate,cobalt nitrate, cupric nitrate, iron nitrate, lead nitrate, potassiumnitrate, nickel nitrate, silver nitrate, strontium nitrate, zincnitrate, nitrate hydrates, and mixtures thereof.

Water-soluble oxalate salts may be selected from the group consisting ofsodium oxalate, chromium oxalate, iron oxalate, potassium oxalate,oxalate hydrates, and mixtures thereof.

Water-soluble sulfite salts may be selected from the group consisting ofammonium sulfite, potassium sulfite, sodium sulfite, magnesium sulfite,sulfite hydrates, and mixtures thereof.

Water-soluble citrate salts may be selected from the group consisting ofpotassium citrate, sodium citrate, magnesium citrate, citrate hydrates,and mixtures thereof.

Water-soluble salts may be selected from the group consisting of watersoluble alkaline earth metal salts, hydrates thereof, and mixturesthereof.

If the carrier granule contains at least one water-soluble phosphate orcarbonate (such as but not limited to soda ash) or sulphite salt, thenthe release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following cations: beryllium,magnesium (such as but not limited to magnesium sulfate, magnesiumchloride), calcium, strontium, barium, radium, scandium, titanium,zirconium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese,iron(II & III), ruthenium, cobalt, iridium, nickel, palladium, platinum,copper (I & II), silver, gold, zinc, cadmium, boron, aluminum, thallium,antimony, bismuth, pyridinium, and mixtures thereof. For example, therelease-rate modifier may be selected from MgSO₄ or MgCl₂, and the like,and combinations thereof.

If the carrier granule contains at least one water-soluble hydroxidesalt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following cations: beryllium,magnesium (such as but not limited to magnesium sulfate, magnesiumchloride), calcium, scandium, titanium, zirconium, hafnium, vanadium,chromium, molybdenum, tungsten, manganese, iron(II & III), ruthenium,cobalt, iridium, nickel, palladium, platinum, copper (I & II), silver,gold, zinc, cadmium, boron, aluminum, antimony, bismuth, pyridinium, andmixtures thereof.

If the carrier granule contains at least one water-soluble sulfide salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following cations: scandium,titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten,manganese, iron(II & III), ruthenium, cobalt, iridium, nickel,palladium, platinum, copper (I & II), silver, gold, zinc, cadmium,boron, aluminum, thallium, antimony, bismuth, pyridinium, and mixturesthereof.

If the carrier granule contains at least one water-soluble sulfate salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following cations: calcium,strontium, barium, silver, lead, radium, and mixtures thereof.

If the carrier granule contains at least one water-soluble chloride orbromide or iodide salt, then the release-rate modifier may be selectedfrom at least one water-soluble salt of at least one of the followingcations: silver, lead, mercury, copper, thallium, and mixtures thereof.

If the carrier granule contains at least one water-soluble aluminumsalt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: hydroxide,oxide, oxalate, phosphate, silicate, and mixtures thereof.

If the carrier granule contains at least one water-soluble ammoniumsalt, then the release-rate modifier may be selected from at least onewater-soluble oxalate salt.

If the carrier granule contains at least one water-soluble antimonysalt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: oxide,oxalate, and mixtures thereof.

If the carrier granule contains at least one water-soluble arsenic salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: oxide,sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble barium salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chromate, oxalate, phosphate, sulfate, sulfite, and mixtures thereof.

If the carrier granule contains at least one water-soluble bismuth salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: acetate,iodide, oxide, phosphate, silicate, sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble cadmium salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chromate, hydroxide, oxide, oxalate, phosphate, silicate, sulfide,sulfite, and mixtures thereof.

If the carrier granule contains at least one water-soluble calcium salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,hydroxide, oxide, oxalate, phosphate, silicate, sulfate, sulfide,sulfite, citrate, and mixtures thereof.

If the carrier granule contains at least one water-soluble chromiumsalt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: hydroxide,iodide, oxide, phosphate, sulfide, sulfite, and mixtures thereof.

If the carrier granule contains at least one water-soluble cobalt salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chromate, hydroxide, oxide, oxalate, phosphate, silicate, sulfide,sulfite, and mixtures thereof.

If the carrier granule contains at least one water-soluble copper salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,hydroxide, oxide, oxalate, phosphate, sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble ferric salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: hydroxide,oxide, phosphate, sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble ferrous salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chromate, hydroxide, oxide, oxalate, phosphate, silicate, sulfite,sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble lead salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: bromide,carbonate, chloride, chromate, hydroxide, iodide, oxide, oxalate,phosphate, silicate, sulfate, sulfite, sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble magnesiumsalt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,hydroxide, oxide, oxalate, phosphate, silicate, and mixtures thereof.

If the carrier granule contains at least one water-soluble mercury(II)salt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: bromide,carbonate, chromate, iodide, oxide, oxalate, sulfide, and mixturesthereof.

If the carrier granule contains at least one water-soluble mercury (I)salt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: acetate,bromide, carbonate, chloride, chromate, iodide, oxide, oxalate, sulfate,sulfide, and mixtures thereof.

If the carrier granule contains at least one water-soluble nickel salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chlorate, hydroxide, oxide, oxalate, phosphate, sulfide, sulfite, andmixtures thereof.

If the carrier granule contains at least one water-soluble silver salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: acetate,bromide, carbonate, chloride, chromate, iodide, oxide, oxalate,phosphate, sulfate, sulfide, sulfite, and mixtures thereof.

If the carrier granule contains at least one water-soluble strontiumsalt, then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chromate, hydroxide, oxide, oxalate, phosphate, silicate, sulfate,sulfide, sulfite, and mixtures thereof.

If the carrier granule contains at least one water-soluble zinc salt,then the release-rate modifier may be selected from at least onewater-soluble salt of at least one of the following anions: carbonate,chromate, hydroxide, oxide, oxalate, phosphate, silicate, sulfide,sulfite, and mixtures thereof.

The amount of water-soluble salt (release-rate modifier) necessary toform the water-insoluble salt coating on the colored speckle may varydepending upon the nature of the salt or salt-containing carriermaterial and the desired performance of the resulting colored speckle.The thickness of the water-insoluble salt coating may affect the speedwith which the coloring agent is released from the granule. A thickercoating layer may prolong the time it takes for the coloring agent torelease from the granule. In comparison, a thinner coating may allow thecoloring agent to release more quickly. As a result, the optimum ratioof salt or salt-containing carrier to release-rate modifier may be thehighest carrier to release-rate modifier ratio at which desiredcontrolled color release is enabled and which does not compromise bleedprotection.

Thus, to effectuate the delayed release of a coloring agent from acarrier granule, a water-insoluble or minimally water-soluble salt maybe applied to a carrier-coloring agent composite. The salt may beapplied to the composite as a uniform coating or as a non-uniformcoating. The water-insoluble or minimally water-soluble salt coatingacts to delay the release of the coloring agent from the carrier. Thisactivity occurs through a reaction between the water-soluble salt(release-rate modifier) and the (water-soluble) salt present in thecarrier agent material or granule to form a water-insoluble salt coatingthereon. The thickness of the coating (or the amount of water-insolubleor minimally water-soluble salt) may affect the speed with which thecoloring agent is released from the granule. A thicker coating layer (orgreater the amount of water-insoluble or minimally water-soluble salt)may prolong the time it takes for the coloring agent to release from thegranule. In comparison, a thinner coating may allow the coloring agentto release more quickly. Thus, the release of coloring agent from thecarrier may be controlled by various factors, such as the thickness ofthe water-insoluble or minimally water-soluble salt coating applied tothe carrier-coloring agent composite.

The water-insoluble salt coating formed on the surface of the coloredspeckle may be prepared by combining two water-soluble salt compounds inan aqueous environment and allowing the salt compounds to react witheach other to form a water-insoluble salt precipitate and/or coating.Thus, one non-limiting method for preparing the water-insoluble saltcoating includes applying a water soluble salt (A) to the surface of agranule comprised of water soluble salt (B) to yield a water-insolubleor minimally water-soluble precipitate of a third salt (C) that resultsin a delay in the release of color (or other active) from the surface orinterior of the salt or salt-containing granule (B).

In one non-limiting embodiment, a colored speckle having delayed releaseof color may be prepared by wetting the surface of a soda ash-basedcarrier-coloring agent composite with a solution of either magnesiumsulfate or magnesium chloride. The soda ash reacts with the magnesiumsulfate salt solution (or magnesium chloride solution) to yield aprecipitate of water-insoluble or minimally water-soluble magnesiumcarbonate that is present as a coating on the surface of thecarrier-coloring agent composite. The coating imparts delayedsolubility, and hence delayed color release, to the soda ash speckle.

One method for forming colored speckles having delayed color releaseproperties includes the steps of providing uncolored carrier granulesand loading the carrier granules into a rotating drum or other suitablemechanical device. Heat may or may not be applied to the drum. The drummay or may not have baffles or other protrusions attached to itsinterior walls.

A coloring agent may be added to the rotating drum. The coloring agentmay be added, preferably in the form of an aqueous solution, to the drumusing any conventional means for adding materials to a container. Forexample, the coloring agent may be sprayed into the drum.

The coloring agent thus comes into contact with the carrier. Thecoloring agent may provide a substantially uniform coating on and/orinto the carrier

Next, the water-soluble salt (the “release-rate modifier”), preferablyin the form of an aqueous solution, may be added to the carrier-coloringagent composite that remains in the rotating drum. The water-solublesalt may be added to the drum using any conventional means for addingmaterials to a container. For example, the water-soluble salt may besprayed into the drum. The water-soluble salt thus comes into contactwith the carrier-coloring agent composite. The water-soluble salt mayprovide a substantially uniform coating on and/or into thecarrier-coloring agent composite (either by itself or throughprecipitation of a salt through reaction with salt/salts in carriergranule or both). The resulting colored speckle may have a finalcolor-on-speckle loading of 0.01% to 10%, more preferably of 0.1% to 5%.

The colored speckles may then be dried. Drying may be accomplished byany conventional means known for drying particulate materials.

The general methods for preparing the colored speckle described hereinmay not be construed as limiting the scope of the present invention. Itshould be possible, by way of alternative processing methods, to combinethe carrier, coloring agent, and water-soluble (release-rate modifier)to produce a colored speckle which exhibits similar delayed colorrelease profiles for the coloring agent, as well as other desiredfeatures, as the colored speckles produced by the general methodsdescribed herein and by their equivalent methods as known to thoseskilled in the art. For instance, it may be possible to combine thecoloring agent and the water-soluble salt (release-rate modifier)together into a mixture and then spray or otherwise apply the mixture tothe carrier. It might also be possible to subsequently add additionalcoloring agent to the carrier to create a colored speckle having aninitial release of color and then having a subsequent, delayed releaseof color. Also, it may be possible that a colored speckle having thedesired characteristics may be manufactured by adding the carrier, thecoloring agent, and the water-soluble salt (release-rate modifier)together in one step. It may also be possible that a colored specklehaving the desired characteristics may be manufactured by adding thecoloring agent to the carrier material prior to granulation (in thepowdered form), granulating this colored powder and then adding thewater-soluble salt (release-rate modifier). It may also be possible thata colored speckle having the desired characteristics may be manufacturedby adding the coloring agent and the releasing agent together in onestep to the carrier material prior to granulation (in the powdered form)followed by granulation.

Thus, in one non-limiting embodiment, the structural arrangement ofcarrier to coloring agent to water-insoluble salt may be achieved byadding a coloring agent to the salt or salt-containing carrier eitherprior-to or during the granulation process such that the resultingcolored granule has color uniformly distributed throughout its body oronly on its surface or non-uniformly distributed throughout its body.For example, in some cases the coloring agent may be added to a soda ashmaterial prior-to or during the granulation process. In this instance,the coloring agent may be distributed uniformly throughout the body ofthe granule.

Alternatively, the structural arrangement of carrier to coloring agentto water-insoluble salt may be achieved by adding a coloring agent tothe salt or salt-containing carrier after the granulation process suchthat the resulting colored granule has color only on its surface ornon-uniformly distributed throughout its body.

Further, in yet another non-limiting embodiment, the structuralarrangement of carrier to coloring agent to water-insoluble salt may beachieved by adding a coloring agent to the inner walls or surfaces ofthe salt or salt-containing granule before application of thewater-insoluble or minimally water-soluble salt.

Thus, a release-rate modifier may be included to form a protectivecoating on the colored speckle to aid in the delayed release of acoloring agent from the speckle. Alternatively, a release-rate modifiermay not be desirable for inclusion, depending upon the end-usecharacteristics of the colored speckle that are needed; as such, thecolored speckle of the present invention may be free-from any protectivecoatings.

Additional Optional Additives

Additional optional additives that may be included in the coloredspeckles include perfumes, pigments, enzymes, bleach activators,bleaches, bleach catalysts, bleach stabilizers, foam regulators (foamboosters and antifoam agents), fluorescent whitening agents, soilrepellents, corrosion inhibitors, soil antiredeposition agents, soilrelease agents, dye transfer inhibitors, builders, complexing agents,ion exchangers, buffering agents, and mixtures thereof. Bleed inhibitorssuch as film forming polymers or polymeric coatings may also beincluded. These additives may be included as one or more additionalcomponents comprising the colored speckle, in addition to the coloringagent and the salt or salt-containing carrier.

Methods for Forming the Colored Speckle Having Substantially UniformColor Throughout

There are several methods that may be employed to obtain a coloredspeckle having a cross-sectional volume that is substantially uniformlycolored by at least one coloring agent (wherein the coloring agent ispresent within the interior surfaces of the carrier material as well ason the exterior surface of the carrier material). The colored specklesmade by the methods described herein have at least one coloring agentsubstantially uniformly distributed throughout the carrier material.

In one aspect, the method includes a preliminary step wherein thecoloring agent is applied to a powdered form of the carrier material(prior to the granulation) followed by subsequent granulation.Alternatively, the coloring agent may be introduced to the carriermaterial during the granulation process. More specifically, the coloredspeckle may be made, for example, by using techniques that includeagglomeration, spray drying, mechanical mixing, extrusion and the like.

The process of agglomeration includes tumbling the carrier material inan enclosed rotating container (such as a rotating drum) while at thesame time being sprayed with a coloring agent and, optionally, anadhesive agent (that may contain the coloring agent). Water solubleadhesive agents that may be used are selected from organic materialssuch as starches (for example, corn starch, tapioca starch, dextrin andother partially hydrolyzed or so-called “water-soluble” starches) andgums (for example, gum tragacanth and other water-soluble gums andwater-soluble glues); inorganic materials such as silicates, andmixtures thereof.

In one aspect, pressure agglomeration may be utilized to form thecolored speckles of the present invention. One example of pressureagglomeration that may be suitable is roller compaction. In thisprocess, the carrier material, the coloring agent, and any otheroptional ingredients are first mixed together to form a colored granularmixture. This material is then forced between two compaction rolls (e.g.cylindrical rollers) that apply a pressure to said mixture so that therotation of the rolls transforms the mixture into a compacted sheetand/or flake. This compacted sheet and/or flake is then broken up toform colored granules or particles. These colored granules or particlesare characterized as having color uniformly distributed throughout theircross-sectional volume.

The compacted sheet and/or flake produced by the pressure agglomerationprocess may be broken up into colored granules or particles by anysuitable method for reducing the size of the sheet and/or flake. Forexample, the sheet and/or flake may be reduced in size by cutting,chopping or breaking the sheet/flake to produce the desired size.Additionally, the colored granules or particles may be subsequentlyexposed to a process which further refines their shape, e.g. such as aprocess which causes the particles to become rounded (to obtain round orspherical granules) according to the diameter size as defined hereinbefore.

Additional steps of tumbling and sieving, as known to those skilled inthe art, may also be employed during this process. The step of tumblingaids the manufacturing process by mechanically abrading the coloredspeckles to achieve relatively uniform size and shape of the speckles.The step of sieving aids the manufacturing process by enabling theseparation of colored speckles according to distinct particle size.

In general, with all other characteristics being relatively equal (colorloading, particle size, etc.), colored speckles made according to themethods described herein (wherein at least one coloring agent is appliedto the carrier material prior to/or during a granulation process) mayexhibit a lower concentration of coloring agent on the exterior surfaceof the speckle, when compared to colored speckles wherein the coloringagent is applied only to the exterior surface of the carrier material(e.g. the coloring agent is sprayed on the exterior surface of thecarrier material). This may be explained by the fact that coloredspeckles of the present invention contain coloring agent distributedthroughout the entire cross-sectional volume of the color speckle,rather than just being present on only the surface of the speckle. Thus,the colored speckles of the present invention may contain a greateramount of colored volume, when compared with the amount of coloredvolume exhibited by similarly sized colored speckles having colorpresent only on the exterior surface of the speckle.

As a result of this difference in coloring agent concentration on theouter surface of the colored speckle, the colored speckles of thepresent invention may exhibit lighter shades of color (e.g. lighterblues shades) when compared with a colored speckle having color presentonly on its exterior surface (e.g. darker blue shades). It mayunexpected that such lighter shades of color would provide enoughaesthetically pleasing color to a detergent composition to which it maybe added, or that these colored speckles would provide enough coloringagent to adequately color the wash water of a detergent-containingsolution, or that these colored speckles would release enoughbluing/hueing agent (color) into the wash water so as to deposit onfabric and provide a whiteness perception benefit.

Laundry Care Compositions

The colored speckles described in the present specification may beincorporated into a laundry care composition including but not limitedto laundry detergents and fabric care compositions. Such compositionscomprise one or more of the colored speckles and a laundry careingredient.

The laundry care compositions including laundry detergents may be insolid or liquid form, including a gel form. The solid form of thelaundry care compositions include, for example, compositions comprisedof granules, powder, or flakes. For instance, the colored speckles ofthe present invention may be added to powdered laundry detergentcompositions.

The colored speckles may be present in a laundry detergent compositionin an amount from about 0.0001% to about 20% by weight of thecomposition, from about 0.0001% to about 10% by weight of thecomposition, and even from about 0.0001% to about 5% by weight of thecomposition.

The laundry detergent composition typically comprises a surfactant in anamount sufficient to provide desired cleaning properties. In oneembodiment, the laundry detergent composition comprises, by weight, fromabout 5% to about 90% of the surfactant, and more specifically fromabout 5% to about 70% of the surfactant, and even more specifically fromabout 5% to about 40%. The surfactant may comprise anionic, nonionic,cationic, zwitterionic and/or amphoteric surfactants. In a more specificembodiment, the detergent composition comprises anionic surfactant,nonionic surfactant, or mixtures thereof.

Fabric care compositions are typically added in the rinse cycle, whichis after the detergent solution has been used and replaced with therinsing solution in typical laundering processes. The fabric carecompositions disclosed herein may be comprise a rinse added fabricsoftening active and one or more colored speckles as disclosed in thepresent specification. The fabric care composition may comprise, basedon total fabric care composition weight, from about 1% to about 90%, orfrom about 5% to about 50% fabric softening active. The colored specklesmay be present in the fabric care composition in an amount from about0.5 ppb to about 50 ppm, or from about 0.5 ppm to about 30 ppm.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain aspects of the invention, for exampleto assist or enhance performance, for treatment of the substrate to becleaned, or to modify the aesthetics of the composition as is the casewith perfumes, colorants, dyes or the like. It is understood that suchingredients are in addition to the components that were previouslylisted for any particular aspect. The total amount of such adjuncts mayrange, once the amount of dye is taken into consideration from about 90%to about 99.99999995% by weight of the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,fabric softening actives, polymers, for example cationic polymers,surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic materials,bleach activators, polymeric dispersing agents, clay soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,additional perfume and perfume delivery systems, structure elasticizingagents, fabric softeners, carriers, hydrotropes, processing aids and/orpigments. In addition to the disclosure below, suitable examples of suchother adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain aspects of Applicants'compositions do not contain one or more of the following adjunctsmaterials: fabric softening actives, bleach activators, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic metal complexes, polymericdispersing agents, clay and soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfumes and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. However, whenone or more adjuncts are present, such one or more adjuncts may bepresent as detailed below:

Surfactants

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀-C₁₆alkyl benzene sulfonic acids, or C₁₁-C₁₄ alkyl benzene sulfonic acids.In one aspect, the alkyl group is linear and such linear alkyl benzenesulfonates are known as “LAS”. Alkyl benzene sulfonates, andparticularly LAS, are well known in the art. Such surfactants and theirpreparation are described for example in U.S. Pat. Nos. 2,220,099 and2,477,383. Especially useful are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., C₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O), —SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In one aspect, R′ isC₁₀-C₁₈ alkyl, n is from about 1 to 15, and M is sodium, potassium,ammonium, alkylammonium, or alkanolammonium. In one aspect, R′ is aC₁₂-C₁₆, n is from about 1 to 6 and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In one aspect, R is aC₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R is C₁₂-C₁₄ andM is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3) alkyl sulfates having formulae (I) and (II): wherein M in formulae(I) and (II) is hydrogen or a cation which provides charge neutrality,and all M units, whether associated with a surfactant or adjunctingredient, can either be a hydrogen atom or a cation depending upon theform isolated by the artisan or the relative pH of the system whereinthe compound is used, with non-limiting examples of suitable cationsincluding sodium, potassium, ammonium, and mixtures thereof, and x is aninteger of at least about 7, or at least about 9, and y is an integer ofat least 8, or at least about 9; d) C₁₀-C₁₈ alkyl alkoxy sulfates(AE_(x)S) wherein x is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylatesin one aspect, comprising 1-5 ethoxy units; f) mid-chain branched alkylsulfates as discussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No.6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed inU.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303; h) modifiedalkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242,WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j)alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. In one aspect, for use in the liquid detergentproducts herein are those nonionic surfactants which are normallyliquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)—OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.In one aspect, R¹ is an alkyl group, which may be primary or secondary,that comprises from about 9 to 15 carbon atoms, or from about 10 to 14carbon atoms. In one aspect, the alkoxylated fatty alcohols will also beethoxylated materials that contain from about 2 to 12 ethylene oxidemoieties per molecule, or from about 3 to 10 ethylene oxide moieties permolecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17 from about 6 to 15, orfrom about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants havebeen marketed under the tradenames Neodol and Dobanol by the ShellChemical Company.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(n)N(O)(CH₂R′)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20, 10 to 16carbon atoms, or is a C₁₂-C₁₆ primary alkyl. R′ is a short-chain moiety,in one aspect R′ may be selected from hydrogen, methyl and —CH₂OH. Whenx+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy andBO is butyleneoxy. Amine oxide surfactants are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856;f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 toLlenado, issued Jan. 26, 1986; specifically alkylpolyglycosides asdiscussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g)Polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528,WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ethercapped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat.No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (in one aspect C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, or C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

Aqueous, Non-Surface Active Liquid Carrier

As noted, the laundry care compositions may be in the form of a solid,either in tablet or particulate form, including, but not limited toparticles, flakes, sheets, or the like, or the compositions may be inthe form of a liquid. The liquid detergent compositions may comprise anaqueous, non-surface active liquid carrier. Generally, the amount of theaqueous, non-surface active liquid carrier employed in the compositionsherein will be effective to solubilize, suspend or disperse thecomposition components. For example, the liquid detergent compositionsmay comprise, based on total liquid detergent composition weight, fromabout 5% to about 90%, from about 10% to about 70%, or from about 20% toabout 70% of the aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier is typically water. Accordingly, the aqueous, non-surface activeliquid carrier component will generally be mostly, if not completely,comprised of water. While other types of water-miscible liquids, suchalkanols, diols, other polyols, ethers, amines, and the like, have beenconventionally been added to liquid detergent compositions asco-solvents or stabilizers, for purposes of the present invention, theutilization of such water-miscible liquids typically is minimized tohold down composition cost. Accordingly, the aqueous liquid carriercomponent of the liquid detergent products herein will generallycomprise water present in concentrations ranging from about 5% to about90%, or from about 5% to about 70%, by weight of the liquid detergentcomposition.

Bleaching Agents

-   -   Bleaching Agents—The laundry care compositions of the present        invention may comprise one or more bleaching agents. Suitable        bleaching agents other than bleaching catalysts include        photobleaches, bleach activators, hydrogen peroxide, sources of        hydrogen peroxide, pre-formed peracids and mixtures thereof. In        general, when a bleaching agent is used, the compositions of the        present invention may comprise from about 0.1% to about 50% or        even from about 0.1% to about 25% bleaching agent by weight of        the subject laundry care composition. Examples of suitable        bleaching agents include:        -   (1) photobleaches for example sulfonated zinc            phthalocyanine;        -   (2) preformed peracids: Suitable preformed peracids include,            but are not limited to, compounds selected from the group            consisting of percarboxylic acids and salts, percarbonic            acids and salts, perimidic acids and salts,            peroxymonosulfuric acids and salts, for example, Oxzone®,            and mixtures thereof. Suitable percarboxylic acids include            hydrophobic and hydrophilic peracids having the formula            R—(C═O)O—O-M wherein R is an alkyl group, optionally            branched, having, when the peracid is hydrophobic, from 6 to            14 carbon atoms, or from 8 to 12 carbon atoms and, when the            peracid is hydrophilic, less than 6 carbon atoms or even            less than 4 carbon atoms; and M is a counterion, for            example, sodium, potassium or hydrogen;        -   (3) sources of hydrogen peroxide, for example, inorganic            perhydrate salts, including alkali metal salts such as            sodium salts of perborate (usually mono- or tetra-hydrate),            percarbonate, persulphate, perphosphate, persilicate salts            and mixtures thereof. In one aspect of the invention the            inorganic perhydrate salts are selected from the group            consisting of sodium salts of perborate, percarbonate and            mixtures thereof. When employed, inorganic perhydrate salts            are typically present in amounts of from 0.05 to 40 wt %, or            1 to 30 wt % of the overall composition and are typically            incorporated into such compositions as a crystalline solid            that may be coated. Suitable coatings include, inorganic            salts such as alkali metal silicate, carbonate or borate            salts or mixtures thereof, or organic materials such as            water-soluble or dispersible polymers, waxes, oils or fatty            soaps; and        -   (4) bleach activators having R—(C═O)-L wherein R is an alkyl            group, optionally branched, having, when the bleach            activator is hydrophobic, from 6 to 14 carbon atoms, or from            8 to 12 carbon atoms and, when the bleach activator is            hydrophilic, less than 6 carbon atoms or even less than 4            carbon atoms; and L is leaving group. Examples of suitable            leaving groups are benzoic acid and derivatives            thereof—especially benzene sulphonate. Suitable bleach            activators include dodecanoyl oxybenzene sulphonate,            decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or            salts thereof, 3,5,5-trimethyl hexanoyloxybenzene            sulphonate, tetraacetyl ethylene diamine (TAED) and            nonanoyloxybenzene sulphonate (NOBS). Suitable bleach            activators are also disclosed in WO 98/17767. While any            suitable bleach activator may be employed, in one aspect of            the invention the subject cleaning composition may comprise            NOBS, TAED or mixtures thereof.

When present, the peracid and/or bleach activator is generally presentin the composition in an amount of from about 0.1 to about 60 wt %, fromabout 0.5 to about 40 wt % or even from about 0.6 to about 10 wt % basedon the composition. One or more hydrophobic peracids or precursorsthereof may be used in combination with one or more hydrophilic peracidor precursor thereof.

The amounts of hydrogen peroxide source and peracid or bleach activatormay be selected such that the molar ratio of available oxygen (from theperoxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

Bleach Boosting Compounds—The compositions herein may comprise one ormore bleach boosting compounds. Bleach boosting compounds provideincreased bleaching effectiveness in lower temperature applications. Thebleach boosters act in conjunction with conventional peroxygen bleachingsources to provide increased bleaching effectiveness. This is normallyaccomplished through in situ formation of an active oxygen transferagent such as a dioxirane, an oxaziridine, or an oxaziridinium.Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums maybe used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

-   -   where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted        radical selected from the group consisting of phenyl, aryl,        heterocyclic ring, alkyl and cycloalkyl radicals.

Suitable bleach boosting compounds include zwitterionic bleach boosterszwitterionic bleach boosters, which are described in U.S. Pat. Nos.5,576,282 and 5,718,614. Other bleach boosting compounds includecationic bleach boosters described in U.S. Pat. Nos. 5,360,569;5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351,WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are typically employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

-   -   Enzyme Bleaching—Enzymatic systems may be used as bleaching        agents. The hydrogen peroxide may also be present by adding an        enzymatic system (i.e. an enzyme and a substrate therefore)        which is capable of generating hydrogen peroxide at the        beginning or during the washing and/or rinsing process. Such        enzymatic systems are disclosed in EP Patent Application        91202655.6 filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No.5,346,588 describes a process for the utilization of ozone as analternative to conventional bleach systems and is herein incorporated byreference.

In one aspect, the fabric softening active (“FSA”) is a quaternaryammonium compound suitable for softening fabric in a rinse step. In oneaspect, the FSA is formed from a reaction product of a fatty acid and anaminoalcohol obtaining mixtures of mono-, di-, and, in one aspect,triester compounds. In another aspect, the FSA comprises one or moresoftener quaternary ammonium compounds such, but not limited to, as amonoalkyquaternary ammonium compound, a diamido quaternary compound anda diester quaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certain aspects ofthe present invention, the DQA compounds compositions also encompasses adescription of diamido FSAs and FSAs with mixed amido and ester linkagesas well as the aforementioned diester linkages, all herein referred toas DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}X⁻

-   -   wherein each R substituent is either hydrogen, a short chain        C₁-C₆, for example C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl, ethyl, propyl, hydroxyethyl, and the like, poly (C₂₋₃        alkoxy), for example. polyethoxy, group, benzyl, or mixtures        thereof; each m is 2 or 3; each n is from 1 to about 4, or 2;        each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR— and it is        acceptable for each Y to be the same or different; the sum of        carbons in each R¹, plus one when Y is —O—(O)C— or —NR—C(O)—, is        C₁₂-C₂₂, or C₁₄-C₂₀, with each R¹ being a hydrocarbyl, or        substituted hydrocarbyl group; it is acceptable for R¹ to be        unsaturated or saturated and branched or linear and in one        aspect it is linear; it is acceptable for each R¹ to be the same        or different and typically these are the same; and X⁻ can be any        softener-compatible anion, suitable anions include, chloride,        bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and        nitrate, in one aspect the anions are chloride or methyl        sulfate. Suitable DQA compounds are typically made by reacting        alkanolamines such as MDEA (methyldiethanolamine) and TEA        (triethanolamine) with fatty acids. Some materials that        typically result from such reactions include        N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or        N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium        methylsulfate wherein the acyl group is derived from animal        fats, unsaturated, and polyunsaturated, fatty acids, e.g.,        tallow, hardended tallow, oleic acid, and/or partially        hydrogenated fatty acids, derived from vegetable oils and/or        partially hydrogenated vegetable oils, such as, canola oil,        safflower oil, peanut oil, sunflower oil, corn oil, soybean oil,        tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one aspect, the FSA comprisesother actives in addition to DQA (1) or DQA. In yet another aspect, theFSA comprises only DQA (1) or DQA and is free or essentially free of anyother quaternary ammonium compounds or other actives. In yet anotheraspect, the FSA comprises the precursor amine that is used to producethe DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:[R_(4-m)—N⁽⁺⁾—R¹ _(m)]A⁻

-   -   wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, or C₁₄-C₂₀, but        no more than one being less than about C₁₂ and then the other is        at least about 16, hydrocarbyl, or substituted hydrocarbyl        substituent, for example, C₁₀-C₂₀ alkyl or alkenyl (unsaturated        alkyl, including polyunsaturated alkyl, also referred to        sometimes as “alkylene”), in one aspect C₁₂-C₁₈ alkyl or        alkenyl, and branch or unbranched. In one aspect, the Iodine        Value (IV) of the FSA is from about 1 to 70; each R is H or a        short chain C₁-C₆, or C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl, ethyl, propyl, hydroxyethyl, and the like, benzyl, or        (R²⁰)₂₋₄H where each R² is a C₁₋₆ alkylene group; and A⁻ is a        softener compatible anion, suitable anions include chloride,        bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or        nitrate; in one aspect the anions are chloride or methyl        sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowedimethylammonium andditallowedimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowedimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one aspect, theFSA comprises other actives in addition to DTTMAC. In yet anotheraspect, the FSA comprises only compounds of the DTTMAC and is free oressentially free of any other quaternary ammonium compounds or otheractives.

In one aspect, the FSA comprises an FSA described in U.S. Pat. Pub. No.2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another aspect, the FSA is one described in U.S.Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith et al.,on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line 51 etseq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one aspect, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one aspect, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another aspect of the invention provides for a rinse added fabricsoftening composition further comprising a cationic starch. Cationicstarches are disclosed in US 2004/0204337 A1. In one aspect, the rinseadded fabric softening composition comprises from about 0.1% to about 7%of cationic starch by weight of the fabric softening composition. In oneaspect, the cationic starch is HCP401 from National Starch.

-   -   Builders—The compositions of the present invention can comprise        one or more detergent builders or builder systems. When present,        the compositions will typically comprise at least about 1%        builder, or from about 5% or 10% to about 80%, 50%, or even 30%        by weight, of said builder. Builders include, but are not        limited to, the alkali metal, ammonium and alkanolammonium salts        of polyphosphates, alkali metal silicates, alkaline earth and        alkali metal carbonates, aluminosilicate builders        polycarboxylate compounds. ether hydroxypolycarboxylates,        copolymers of maleic anhydride with ethylene or vinyl methyl        ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and        carboxymethyl-oxysuccinic acid, the various alkali metal,        ammonium and substituted ammonium salts of polyacetic acids such        as ethylenediamine tetraacetic acid and nitrilotriacetic acid,        as well as polycarboxylates such as mellitic acid, succinic        acid, oxydisuccinic acid, polymaleic acid, benzene        1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and        soluble salts thereof.    -   Chelating Agents—The compositions herein may also optionally        contain one or more copper, iron and/or manganese chelating        agents. If utilized, chelating agents will generally comprise        from about 0.1% by weight of the compositions herein to about        15%, or even from about 3.0% to about 15% by weight of the        compositions herein.    -   Dye Transfer Inhibiting Agents—The compositions of the present        invention may also include one or more dye transfer inhibiting        agents. Suitable polymeric dye transfer inhibiting agents        include, but are not limited to, polyvinylpyrrolidone polymers,        polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and        N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles        or mixtures thereof. When present in the compositions herein,        the dye transfer inhibiting agents are present at levels from        about 0.0001%, from about 0.01%, from about 0.05% by weight of        the cleaning compositions to about 10%, about 2%, or even about        1% by weight of the cleaning compositions.    -   Dispersants—The compositions of the present invention can also        contain dispersants. Suitable water-soluble organic materials        are the homo- or co-polymeric acids or their salts, in which the        polycarboxylic acid may comprise at least two carboxyl radicals        separated from each other by not more than two carbon atoms.    -   Enzymes—The compositions can comprise one or more detergent        enzymes which provide cleaning performance and/or fabric care        benefits. Examples of suitable enzymes include, but are not        limited to, hemicellulases, peroxidases, proteases, cellulases,        xylanases, lipases, phospholipases, esterases, cutinases,        pectinases, keratanases, reductases, oxidases, phenoloxidases,        lipoxygenases, ligninases, pullulanases, tannases, pentosanases,        malanases, β-glucanases, arabinosidases, hyaluronidase,        chondroitinase, laccase, and amylases, or mixtures thereof. A        typical combination is a cocktail of conventional applicable        enzymes like protease, lipase, cutinase and/or cellulase in        conjunction with amylase.    -   Enzyme Stabilizers—Enzymes for use in compositions, for example,        detergents can be stabilized by various techniques. The enzymes        employed herein can be stabilized by the presence of        water-soluble sources of calcium and/or magnesium ions in the        finished compositions that provide such ions to the enzymes.        Process of Making

The liquid detergent compositions are in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, colored speckles, andcertain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable and will typically have a viscosity which rangesfrom about 100 to 600 cps, or from about 150 to 400 cps. For purposes ofthis invention, viscosity is measured with a Brookfield LVDV-II+viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, or even substantially all, of the liquid components, e.g.,nonionic surfactant, the non-surface active liquid carriers and otheroptional liquid components, with the liquid components being thoroughlyadmixed by imparting shear agitation to this liquid combination. Forexample, rapid stirring with a mechanical stirrer may usefully beemployed. While shear agitation is maintained, substantially all of anyanionic surfactants and the solid form ingredients can be added.Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In one aspect of forming the liquid detergent compositions, the coloredspeckles are first combined with one or more liquid components to form acolored speckle premix, and this premix is added to a compositionformulation containing a substantial portion, for example more than 50%by weight, more specifically, more than 70% by weight, and yet morespecifically, more than 90% by weight, of the balance of components ofthe laundry detergent composition. For example, in the methodologydescribed above, both the colored speckle premix and the enzymecomponent are added at a final stage of component additions. In anotheraspect, the colored speckles are encapsulated prior to addition to thedetergent composition, the encapsulated speckles are suspended in astructured liquid, and the suspension is added to a compositionformulation containing a substantial portion of the balance ofcomponents of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles, flakes or sheets. Various techniques for formingdetergent compositions in such solid forms are well known in the art andmay be used herein. In one aspect, for example when the detergentcomposition is in the form of a granular particle, the colored specklesare provided in particulate form, optionally including additional butnot all components of the laundry detergent composition. The coloredspeckles are combined with one or more additional particulatescontaining a balance of components of the laundry detergent composition.Further, the colored speckles, optionally including additional but notall components of the laundry detergent composition, may be provided inan encapsulated form, and the colored speckle encapsulate is combinedwith particulates containing a substantial balance of components of thelaundry detergent composition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof fabrics. Generally, an effective amount of such compositions is addedto water, for example in a conventional fabric laundering automaticwashing machine, to form such aqueous laundering solutions. The aqueouswashing solution so formed is then contacted, typically under agitation,with the fabrics to be laundered therewith. An effective amount of theliquid detergent compositions herein added to water to form aqueouslaundering solutions can comprise amounts sufficient to form from about500 to 7,000 ppm of composition in aqueous washing solution, or fromabout 1,000 to 3,000 ppm of the detergent compositions herein will beprovided in aqueous washing solution.

Method of Use

Certain of the consumer products disclosed herein can be used to cleanor treat a situs inter alia a surface or fabric. Typically at least aportion of the situs is contacted with an embodiment of Applicants'consumer product, in neat form or diluted in a liquor, for example, awash liquor and then the situs may be optionally washed and/or rinsed.In one aspect, a situs is optionally washed and/or rinsed, contactedwith an aspect of the consumer product and then optionally washed and/orrinsed. For purposes of the present invention, washing includes but isnot limited to, scrubbing, and mechanical agitation. The fabric maycomprise most any fabric capable of being laundered or treated in normalconsumer use conditions. Liquors that may comprise the disclosedcompositions may have a pH of from about 3 to about 11.5. Suchcompositions are typically employed at concentrations of from about 500ppm to about 15,000 ppm in solution. When the wash solvent is water, thewater temperature typically ranges from about 5° C. to about 90° C. and,when the situs comprises a fabric, the water to fabric ratio istypically from about 1:1 to about 30:1. Employing one or more of theaforementioned methods results in a treated situs.

EXAMPLES

The invention may be further understood by reference to the followingexamples which are not to be construed as limiting the scope of thepresent invention. The indication of “N/A” is used when no data or noadditional data is available.

The following examples were prepared to illustrate that, at equal colorloadings and particle size, colored speckles prepared according to themethods of the present invention consistently provided better bleedprotection when tested in granular detergent compositions.

A. Preparation of Colored Speckles

The following procedures were used to prepare colored speckles:

Colored Speckle Preparation (Method A)

-   -   1. 50 g of ungranulated sodium carbonate powder (Light E Grade        from Brunner Mond) was added to a small food processor.    -   2. The desired amount of coloring agent was added to a small        beaker and diluted with water, as indicated in Table 1. This        colored aqueous solution was then dripped into the food        processor and blended into the powder. After all of the colored        aqueous solution was added and blended, the colored powder was        spread out onto a piece of foil overnight to dry.    -   3. The colored powder was then compacted in a tablet press. Two        10 g tablets were made using 10,000 pounds of pressure for about        5 seconds.    -   4. The tablets were then broken into big chunks with a hammer.        The big chunks were put back into the small food processor and        chopped into smaller pieces. The colored speckles thus produced        were then sifted through #14 and #25 sieves. The speckles that        would not go through the #25 were kept.    -   5. These colored speckles are provided as Examples 1 through 10        in Table 1A.

TABLE 1A Colored speckles made according to Method A. Amount of AmountAmount Coloring of of Sodium Coloring % Color Agent Water CarbonateSample Agent Wt. Value (g) (g) (g) Example 1 Violet DD^(a) 3 4.5 1.61 250 (PP012) Example 2 Direct 3.6 3.75 1.932 2 50 Violet 9^(b) Example 3Acid 0.716 19.32 0.375 7 50 Blue 80^(c) (01001) Example 4 Acid 0.16385.31 0.085 2 50 Red 52^(d) Example 5 Ultramarine 0.952 NA 0.5 2 50Blue^(e) Example 6 Blue SE^(a) 0.952 14.5 0.5 2 50 Example 7 Direct 0.2458.22 0.125 2 50 Blue 86^(f) Example 8 Pigment 0.952 NA 0.5 2 50 Blue 15Example 9 Chromatint 0.952 NA 0.5 2 50 Yellow X-2407^(g) ExamplePhotoBleach 0.952 NA 0.5 2 50 10 ^(a)Liquitint ® polymeric colorant,available from Milliken & Company of Spartanburg, SC. ^(b)A direct dye,available from Ciba. ^(c)An acid dye, available from Aceto. ^(d)An aciddye, available from Color Chem (Clariant). ^(e)A pigment, available fromBrenntag Specialties. ^(f)A direct dye, available from Blackman Uhler.^(g)A colorant, available from Chromatech Incorporated.

Colored Speckle Preparation (Method B)

-   -   1. 50 g of granulated soda ash (available from Brunner Mond) was        sifted through #14 and #25 sieves. The speckles that would not        go through the #25 were retained. These speckles were then put        into the tumble mixer.    -   2. The desired amount of coloring agent was added to a small        beaker and diluted with water, as indicated in Table 1. This        colored aqueous solution was then sprayed with an airbrush onto        the granulated soda ash.    -   3. The resulting colored speckles were then spread out on a        piece of foil to dry overnight.    -   4. These colored speckles are provided as Comparative Examples 1        through 10 in Table 1B.

TABLE 1B Colored speckles made according to Method B. Amount of AmountColoring of Amount Coloring Color Agent Water of soda Sample Agent % wt.Value (g) (g) ash (g) Comparative Violet DD^(a) 3 4.5 1.61 5 50 Example1 (PP012) Comparative Direct 3.6 3.75 1.932 5 50 Example 2 Violet 9^(b)Comparative Acid Blue 0.716 19.32 0.375 7 50 Example 3 80^(c) (01001)Comparative Acid Red 0.163 85.31 0.085 6.3 50 Example 4 52^(d)Comparative Ultamarine 0.952 NA 0.5 6 50 Example 5 Blue^(e) ComparativeBlue SE^(a) 0.952 14.5 0.5 5 50 Example 6 Comparative Direct Blue 0.2458.22 0.125 5 50 Example 7 86^(f) Comparative Pigment 0.952 NA 0.5 5 50Example 8 Blue 15 Comparative Chromatint 0.952 NA 0.5 5 50 Example 9Yellow X- 2407^(g) Comparative PhotoBleach 0.952 NA 0.5 5 50 Example 10^(a)Liquitint ® polymeric colorant, available from Milliken & Company ofSpartanburg, SC. ^(b)A direct dye, available from Ciba. ^(c)An acid dye,available from Aceto. ^(d)An acid dye, available from Color Chem(Clariant). ^(e)A pigment, available from Brenntag Specialties. ^(f)Adirect dye, available from Blackman Uhler. ^(g)A colorant, availablefrom Chromatech Incorporated.B. Test Methods

Color Loading

The following test procedure was used to quantitatively determine thecolor loading of the colored speckles made according to Method A andMethod B, as described herein:

-   -   1. Colored speckles made according to Method A were weighed into        a volumetric flask which was then filled with 50 mL of        de-ionized water.    -   2. The solution was shaken and allowed to sit for about 3 hours.    -   3. After this time expired, the flask was filled to 100 mL with        MeOH.    -   4. A blank was prepared using 50 mL water diluted to 100 mL with        MeOH.    -   5. These solutions were then read on a Beckman Coulter, DU 800        UV-Vis spectrophotometer. Absorbance readings of the solutions        were carried out in a 1 cm path-length quartz cuvette.    -   6. This test method was repeated for the colored speckles made        according to Method B.

It was noted that the de-ionized water dissolved the soda ash carrier,whereas the MeOH was used as a solvent for the coloring agent (MeOH wasnot added for water soluble coloring agents). A ratio of the Absorbancevalues adjusted for sample weight close to 1 indicated equal weightpercent color loading on the speckles made via the two different methods(Method A and Method B). Test results are provided in Table 2.

Bleed Resistance Test

This test compares the bleed resistance of the colored speckles. Eachsample tested for bleed resistance was prepared by adding 2 grams of thecolored speckles to 50 grams of two different powder laundrydetergents—Ariel and Everyday Elegance (commercially available fromProcter & Gamble and Wal-Mart, respectively). Each of the mixtures wasthen placed in an unlined cardboard box in a controlled environment at70% relative humidity and 37° C. for one week.

Each sample was then visually evaluated for the amount of color bleedthat was observed to occur in the surrounding powder laundry detergent.A panel of 10 people evaluated the samples by comparing Example X withthe corresponding Comparative Example X (e.g. Example 1 was comparedwith Comparative Example 1). One point was awarded against the samplethat appeared to have more bleeding into the surrounding detergent. Thesample having less bleeding received zero points. If the evaluator couldnot visually observe a difference in bleed between Example X andComparative Example X, then both samples were awarded zero points. Thus,samples evaluated having lower scores exhibited better bleed resistance.Test results are provided in Table 3.

C. Test Results

Color Loading

The test results for the determination of color loading are provided inTable 2. The ratio of color loading was calculated for each sample asfollows:

$\text{Ratio of Color Loading} = \frac{\frac{\text{Comparative Ex. Absorbance Value}}{\text{Comparative Ex. Sample Weight}}}{\frac{\text{Example Absorbance Value}}{\text{Example Sample Weight}}}$

TABLE 2 Color Loading for Colored Speckles Ratio of Color SampleAbsorbance Color Value Loading Coloring Weight (Optical (lambda onSample Agent (g) Density/cm) max in nm) speckles Example 1 Violet DD0.3036 0.2592 569.5 1.235 (PP012) Comparative Violet DD 0.3320 0.3502570.0 Example 1 (PP012) Example 2 Direct 0.4781 0.5455 562.5 0.987Violet 9 Comparative Direct 0.5183 0.5840 562.0 Example 2 Violet 9Example 3 Acid Blue 0.4356 0.5527 627.0 0.977 80 (01001) ComparativeAcid Blue 0.4336 0.5374 627.5 Example 3 80 (01001) Example 6 Blue SE0.3848 0.5115 635.5 0.975 Comparative Blue SE 0.3820 0.4949 635.5Example 6 Example 7 Direct 0.3636 0.4006 668.0 0.972 Blue 86 ComparativeDirect 0.7145 0.7651 668.0 Example 7 Blue 86

As shown in Table 2, the ratio of the Absorbance values adjusted forsample weight are close to a value of 1, which indicates that thecolored speckles contain approximately equal weight percent colorloading regardless of the method used to make the speckles (Method A andMethod B).

Bleed Resistance

The test results for the determination of bleed resistance are providedin Table 3.

TABLE 3 Bleed Resistance of Colored Speckles Everyday Elegance ArielLaundry Laundry Detergent Detergent Coloring Bleed Resistance BleedResistance Sample Agent Evaluation Value Evaluation Value Example 1Violet DD 0 0 (PP012) Comparative Violet DD 7 10 Example 1 (PP012)Example 2 Direct 0 0 Violet 9 Comparative Direct 7 10 Example 2 Violet 9Example 3 Acid Blue 1 0 80 (01001) Comparative Acid Blue 2 9 Example 380 (01001) Example 5 Ultramarine 0 0 Blue Comparative Ultramarine 1 2Example 5 Blue Example 6 Blue SE 1 0 Comparative Blue SE 1 10 Example 6Example 7 Direct Blue 1 0 86 Comparative Direct Blue 2 3 Example 7 86Example 8 Pigment 4 0 Blue 15 Comparative Pigment 1 2 Example 8 Blue 15Example 9 Chromatint 1 3 Yellow-X 2407 Comparative Chromatint 5 4Example 9 Yellow-X 2407

The test results in Table 3 illustrate that most observers saw anoticeable improvement in bleed resistance for colored speckles madeaccording Method A, as opposed to method B, for at least one of thedetergents utilized in this test. In many instances, improvements inbleed resistance were observed for colored speckles made by Method A inboth detergents. Method A. involved the use of pressure granulation(akin to roller compaction) to agglomerate colored powder. Method Binvolved spraying the coloring agent on the outside of pre-granulatedspeckles.

Thus, the above description and examples show that the inventive coloredspeckles, wherein the coloring agent is present throughout thecross-section of the colored speckle, exhibit improved bleed resistancein granular or powder detergent formulations with which they may becombined. As has been described herein, the inventive colored specklespossess a significant advantage over currently available coloredspeckles by exhibiting improved bleed resistance when added to granulardetergent formulations, while also exhibiting the characteristics ofbeing non-staining to textile materials and also providing good releaseof the coloring agent into wash water. As such, the present coloredspeckles represent a useful advance over the prior art.

These and other modifications and variations to the present inventionmay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present invention.Furthermore, those of ordinary skill in the art will appreciate that theforegoing description is by way of example only, and is not intended tolimit the scope of the invention described in the appended claims.

It is claimed:
 1. A colored speckle consisting essentially of: a) amajority by weight of compacted soda ash carrier material; and b) atleast one coloring agent; wherein the compacted soda ash carriermaterial and the at least one coloring agent form a carrier-coloringagent composite, and wherein the carrier-coloring agent compositecomprises a cross-sectional volume that is uniformly colored by the atleast one coloring agent.
 2. The colored speckle of claim 1, wherein thecoloring agent is selected from the group consisting of polymericcolorants, acid dyes, basic dyes, direct dyes, solvent dyes, vat dyes,mordant dyes, indigoid dyes, reactive dyes, disperse dyes, sulfur dyes,fluorescent dyes, inorganic pigments, organic pigments, naturalcolorants, and mixtures thereof.
 3. The colored speckle of claim 2,wherein the coloring agent is a polymeric colorant.
 4. The coloredspeckle of claim 3, wherein the polymeric colorant is characterized byhaving a chromophore group is selected from the group consisting ofnitroso, nitro, azo and metal complexes thereof, stilbene, bis-stilbene,biphenyl, oligophenethylene, fluorene, coumarin, naphthalamide,diarylmethane, triarylmethane, xanthene acridine, quinoline, methane,polymethine, thiazole, indamine, indophenol, azine, thiazine, oxazine,aminoketone, hydroxyketone, anthraquinone, thioindigoid, phthalocyaninechromophore groups, and mixtures thereof.
 5. A powdered detergentformulation comprising the colored speckle of claim 1.